Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Here...Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N_(2)-bidentate(note that N_(2)-bidentate site=N^N-bidentate site;N_(2)≠dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N_(2)-bidentate site,a Cu SAC with isolated undercoordinated Cu-N_(2) sites(Cu1.0/N_(2)-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N_(2)-GDY exhibits the highest Faradaic efficiency(FE)of 80.6% for CH_(4) in electrocatalytic reduction of CO_(2) at-0.96 V vs.RHE,and the partial current density of CH_(4) is 160 mA cm^(-2).The selectivity for CH_(4) is maintained above 70% when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N_(2)-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N_(2) sites are more favorable in generating key ^(*)COOH and ^(*)CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N_(2) sites toward efficient electrocatalysis.展开更多
Atmospheric pressure plasma jet(APPJ)was used to clean nitrogen-containing carbon films(C–N)fabricated by plasma-assisted chemical vapor deposition method employing the plasma surface interaction linear device at Sic...Atmospheric pressure plasma jet(APPJ)was used to clean nitrogen-containing carbon films(C–N)fabricated by plasma-assisted chemical vapor deposition method employing the plasma surface interaction linear device at Sichuan University(SCU-PSI).The properties of the contaminated films on the surface of pristine and He-plasma pre-irradiated tungsten matrix,such as morphology,crystalline structure,element composition and chemical structure were characterized by scanning electron microscopy,grazing incidence x-ray diffraction and x-ray photoelectron spectroscopy.The experimental results revealed that the removal of C–N film with a thickness of tens of microns can be realized through APPJ cleaning regardless of the morphology of the substrates.Similar removal rates of 16.82 and 13.78μm min^(-1)were obtained for C–N films deposited on a smooth pristine W surface and rough fuzz-covered W surface,respectively.This is a remarkable improvement in comparison to the traditional cleaning method.However,slight surface oxidation was found after APPJ cleaning,but the degree of oxidation was acceptable with an oxidation depth increase of only 3.15 nm.Optical emission spectroscopy analysis and mass spectrometry analysis showed that C–N contamination was mainly removed through chemical reaction with reactive oxygen species during APPJ treatment using air as the working gas.These results make APPJ cleaning a potentially effective method for the rapid removal of C–N films from the wall surfaces of fusion devices.展开更多
Organic electrode materials are desirable for green and sustainable Li-ion batteries(LIBs) due to their light-weight, low cost, abundance and multi-electron transfer reactions during battery operation. However, the su...Organic electrode materials are desirable for green and sustainable Li-ion batteries(LIBs) due to their light-weight, low cost, abundance and multi-electron transfer reactions during battery operation. However, the successful utilization of organic electrodes is hindered by their poor electrical conductivity and low cyclic stability. Herein, a facile synthesis of π-conjugated N-containing heteroaromatic hexacarboxylate(Li6-HAT) compound and its electrochemical performance as an anode material in LIBs is reported.The as-synthesized Li6-HAT electrode renders an ultrahigh initial capacity of 1126.3 m Ah g^(-1) at the current density of 100 m A g^(-1). Moreover, π-conjugated N-containing heteroaromatic center provide excellent reversibility of(de)lithiation process, resulting in excellent capacity retention. Furthermore, a combination of density functional theory(DFT) calculations, in-situ Fourier transform infrared(FTIR) and ex-situ X-ray photoelectron spectroscopy(XPS) characterization reveal that the π-conjugated nitrogen and carboxyl oxygen act as electrochemically active sites during the charge/discharge process. The current work provides novel insights into the charge storage mechanism of organic electrodes and opens up avenues for further development and utilization of organic electrodes in Li-ion batteries.展开更多
N-containing Ce_(2)Si_(2.5)Al_(0.5)O_(3.5)N_(3.5)(CeSiAlON) melilite was synthesized at 1550 and 1600℃ for 5 h from CeO_(2),Si,Al,and Al_(2)O_(3) in nitrogen by using Y_(2)O_(3) and transition-metal nitrates(Co(NO_(3...N-containing Ce_(2)Si_(2.5)Al_(0.5)O_(3.5)N_(3.5)(CeSiAlON) melilite was synthesized at 1550 and 1600℃ for 5 h from CeO_(2),Si,Al,and Al_(2)O_(3) in nitrogen by using Y_(2)O_(3) and transition-metal nitrates(Co(NO_(3))_(2)·6 H_(2) O and Ni(NO_(3))_(2)·6 H_(2)O) as additives.The effects of Y_(2)O_(3) and transition-metal nitrates on the phase,microstructures and photoluminescence properties of CeSiAlON melilite were studied.The incorporation of Y_(2)O_(3) can promote the reaction of raw materials to a low degree,and results in a unit cell shrinkage of CeSiAlON due to the smaller radius of Y atom than that of Ce atom.The transition-metal nitrates can accelerate the reaction clearly and facilitate the formation of CeSiAlON fibers.The photoluminescence(PL) properties of CeSiAlON melilite presents a board violet emission band because of the 5 d-4 f transitions of Ce^(3+),and the additives can enhance the PL emission intensities of specimen significantly.展开更多
Catalytic transformation of renewable biomass into value-added chemicals is an appealing strategy to upgrade bio-mass resources.Due to the presence of abundant oxygen-containing groups such as hydroxyl and aldehyde,bi...Catalytic transformation of renewable biomass into value-added chemicals is an appealing strategy to upgrade bio-mass resources.Due to the presence of abundant oxygen-containing groups such as hydroxyl and aldehyde,biomass and its derived platform molecules have been served as ideal starting feedstock to synthesize valuable N-containing chemicals through reductive amination.In this mini review,we overviewed the recent advances in the reductive ami-nation of several key bio-platform molecules including hydroxyl carboxylic acids,furfural,5-hydroxylmethyl furfural and levulinic acid,with a focus on the production of amino acids,furan amines and pyrrolidones using thermocataly-sis,electrocatalysis or photocatalysis.Moreover,the functions of active sites and the reaction mechanisms in different catalytic systems are discussed to get insights into the key factors in the reductive amination of biomass resources.展开更多
Two N-containing borates, BTES and BMES, were synthesized with dodecyl phenol, 2-(N-containing heterocyclic) ethan-1-ol, boric acid, and dibutylamine, and their tribological properties in rapeseed oil(RSO) were invest...Two N-containing borates, BTES and BMES, were synthesized with dodecyl phenol, 2-(N-containing heterocyclic) ethan-1-ol, boric acid, and dibutylamine, and their tribological properties in rapeseed oil(RSO) were investigated using a four-ball tester. The results showed that the load-carrying ability(P_B value) of RSO can be improved by 40.9% and 67.9%, respectively, when using 0.5 wt% BTES and BMES. Moreover, the antiwear and friction-reducing performances of the additive-containing oils increased with the additive concentration. The X-ray photoelectron spectroscopy results of the worn steel ball surfaces showed that BTES and BMES formed protective films, which contained boron oxide, iron oxide, ferrous sulfate, ferrous sulfide(for BMES), and other organic nitrogen compounds, on the metal surfaces. The better load-carrying and antiwear performances of BMES than those of BTES might be due to their different sulfur contents, which result in different tribochemical reaction films on the contact surfaces. The oxidation stability tests showed that BTES and BMES possessed synergistic antioxidation activity with N-phenyl-α-naphthylamine(T531), and consequently, the oxidation activation energy of the oil sample increased by 77.85% and 82.19%, respectively, compared with that of RSO when the oil sample contained 0.05 wt% BTES/BMES and 0.25% T531.展开更多
Paired electrolysis in anion-exchange membrane(AEM)electrolyzers toward the cathodic nitrate reduction reaction(NO_(3)RR)and anodic benzylamine oxidation reaction(BOR)could generate high value-added N-containing compo...Paired electrolysis in anion-exchange membrane(AEM)electrolyzers toward the cathodic nitrate reduction reaction(NO_(3)RR)and anodic benzylamine oxidation reaction(BOR)could generate high value-added N-containing compounds simultaneously.The key challenge is to develop bifunctional electrocatalysts with a wide potential window,which can achieve highly efficient conversion of anode and cathode reactants.Herein,Ni_(3)Se_(4)with Se vacancies was prepared and employed as the cathode and anode of AEM electrolyzers for NO_(3)RR and BOR.^(15)N isotope-labeling online differential electrochemical mass spectrometry(DEMS)proved that ammonium was reduced from nitrates and revealed the reaction pathway of NO_(3)RR.The density functional theory calculation clarified that Se vacancies regulate d-band centers,and then further modulate the adsorption energy of adsorbed hydrogen,NO_(3)^(-)and intermediates on the Ni_(3)Se_(4)-60s surface in NO_(3)RR,so as to optimize the hydrogenation of NO_(3)^(-)into ammonia.Moreover,during the BOR,the Se vacancy can promote the adsorption of OH^(-),which is easier to form the active species of Ni OOH.The technical and economic evaluation exhibited that the cost of paired electrolysis is 1.21 times lower and the profit is 1.42 times higher than that of the unpaired electrolysis,which shows the economic attraction of paired electrolysis.This work delivers the guidance for the design of efficient catalysts for paired electrolysis in AEM electrolyzer toward the sustainable synthesis of value-added chemicals.展开更多
Evaluating the hydrocarbon generation potential of highly mature organic matter is a key and critically challenging area of research in petroleum geochemistry. To explore this issue, we used negative ion electrospray ...Evaluating the hydrocarbon generation potential of highly mature organic matter is a key and critically challenging area of research in petroleum geochemistry. To explore this issue, we used negative ion electrospray ionization-Fourier transform-ion cyclotron resonance-mass spectrometry to investigate the molecular evolution of N-containing compounds in Carboniferous-lower Permian source rocks with a range of maturities in the northwestern Junggar Basin, China. The N1compounds formed from on-fluorescent chlorophyll catabolites(NCCs), which record the characteristics of the residual soluble organic matter. These components remain in the source rocks after hydrocarbon generation and expulsion, and enable evaluation of the hydrocarbon generation potential. The newly defined indexes of molecular evolution, which are the polymerization index P1([DBE 18+DBE 15]/[DBE 12+DBE 9]_N1) and alkylation index R1(RC_(6–35)/RC_(0–5)), combined with the vitrinite reflectance(VR_(o)) and paleo-salinity index(β-carotane/n Cmax), can identify the factors that control the evolution of highly mature organic matter. The main factor for source rocks deposited in a weakly saline environment is the maturity, but for a highly saline environment both the maturity and salinity are key factors. The high salinity inhibits the molecular polymerization of organic matter and extends the oil generation peak. Given the differences in the bio-precursors in saline source rocks, we propose a new model for hydrocarbon generation that can be used to determine the oil generation potential of highly mature organic matter.展开更多
Herein,a tandem electrocatalytic-catalytic method is employed to produce valuable alanine from nitrate and waste polylactic acid(PLA).Initially,two strategies are proposed to enhance the performance of electrocatalyti...Herein,a tandem electrocatalytic-catalytic method is employed to produce valuable alanine from nitrate and waste polylactic acid(PLA).Initially,two strategies are proposed to enhance the performance of electrocatalytic NO_(3)^(-)reduction reaction(NO_(3)^(-)RR):optimizing NO_(3)^(-)adsorption and accelerating water dissociation by modulating the cathode electrocatalyst.Fe-regulated Co nanosheets(Fe_(0.33)-Co(OH)_(2)NSs)have been developed as an efficient electrocatalyst,which demonstrate a remarkable Faradaic efficiency(FE)of 98.2%,with a corresponding yield rate of 10.7 mg h^(-1)cm^(-2)for NO_(3)RR to NH_(3)at-0.1 V vs.RHE.Additionally,~95%FEs of NH_(3)at-200 mA cm^(-2)have been maintained for>430 h in the alkaline solution.Subsequently,in situ technologies have been utilized to elucidate the NO_(3)^(-)RR pathways,the structure transformation of the electrocatalysts,and the effects of Fe-induced work function reduction and electron enrichment at Co sites on electrocatalytic activity.Finally,alanine is synthesized by using PLA and the generated NH_(3)as the raw reactants on the Ru/TiO_(2)catalyst,achieving maximum yield and selectivity of 81.3%and 91.8%,respectively,which provides a novel approach to utilize the nitrogen resource and mitigate plastic pollution.展开更多
Sarglanoids A-F,six new sesquiterpenoids belonging to eudesmane(1-5)and eremophilane(6)types,were isolated from the leaves of Sarcandra glabra,a famous traditional Chinese medicine(TCM).Their structures including abso...Sarglanoids A-F,six new sesquiterpenoids belonging to eudesmane(1-5)and eremophilane(6)types,were isolated from the leaves of Sarcandra glabra,a famous traditional Chinese medicine(TCM).Their structures including absolute configurations were elucidated through extensive spectroscopic analysis and electronic circular dichroism(ECD)calculations.Compounds 1-2 were rare N-containing eudesmane-type sesquiterpenoids.Compound 3 exhibited inhibitory activity against nitric oxide(NO)production in lipopolysaccharides(LPS)-induced RAW 264.7 cells with IC_(50) values at 20.00±1.30μmol·L^(-1).These findings provide scientific evidence for sesquiterpenoids as the material foundation of S.glabra.展开更多
Heteroatom-doping of carbocatalysts has been a powerful strategy to remarkably enhance the catalytic performance.Herein,the underlying nature of N promotional effects on peroxymonosulfate(PMS)activation for phenol rem...Heteroatom-doping of carbocatalysts has been a powerful strategy to remarkably enhance the catalytic performance.Herein,the underlying nature of N promotional effects on peroxymonosulfate(PMS)activation for phenol removal is understood by combining kinetics analysis with multiple techniques.A strategy using mixed acid oxidation of carbon nanotube(CNT)followed by NH3 treatment is employed to yield a series of catalysts with different N-doping contents but similar fraction of sp^(2)-hybridized carbon and defective degree,endowing with a chance to discriminate the dominant N-containing active sites.The multi-sites kinetics analysis suggests the graphitic N-containing sites as the dominant active sites.The mechanism of the surface-bound reactive species is also discriminated as the dominant reaction mechanism.The insights reported here could provide the methodology to fundamentally understand the heteroatom-doping effects of carbocatalysis.展开更多
The title compound, [Cu（phen）2（SO4）（H2O）]·0.5C4H4O4·7H2O （phen = 1,10-phe-nan throline and C4H4O4 = fumaric acid）, has been synthesized and characterized by single-crystal X-ray diffraction. The crys...The title compound, [Cu（phen）2（SO4）（H2O）]·0.5C4H4O4·7H2O （phen = 1,10-phe-nan throline and C4H4O4 = fumaric acid）, has been synthesized and characterized by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1^- with a = 11.4827（2）, b = 11.9086（2）, c = 13.77350（10） A, α = 80.6830（10）, β = 66.6480（10）, γ = 64.048000）°, V = 1554.63（4） A^3, Mr = 722.17, Z = 2, Dc = 1.543 g/cm^3,μ = 0.845 mm^-1, F（000） = 750, R = 0.0349 and wR = 0.0837 for 4754 observed reflections （1 〉 2σ（I））. The compound contains a six-coordinated copper（Ⅱ） center, which is surround by four N atoms of two phen ligands （Cu-N distances in the range of 1.997（2）- 2.225（2） A）, one sulfate O atom （Cu-O = 2.0037（17） A） and one water O atom （Cu-O（Sw） = 2.719（2） A,） in a distorted octahedral geometry. Extensive hydrogen-bonding interactions are involved in water molecules, ligated sulfate anions and fumaric acid molecules. In addition, π-π interactions via aromatic nitrogen-containing ligands are also discussed. The combination of non-covalent interactions leads to the formation of a 3-D network structure.展开更多
In this work,hydrothermal technique combined with KOH activation were employed to develop a series of porous carbons (NPCK-x) using tobacco stem as a low-cost carbon source and (NH_(4))_(2)C_(2)O_(4)as a novel nitroge...In this work,hydrothermal technique combined with KOH activation were employed to develop a series of porous carbons (NPCK-x) using tobacco stem as a low-cost carbon source and (NH_(4))_(2)C_(2)O_(4)as a novel nitrogen-doping agent.Physicochemical properties of NPCK-x were characterized by Brunauer-Emmett-Teller,field emission scanning electron microscopy,X-ray diffraction,Raman microscope,elemental analysis,and X-ray photoelectron spectroscopy.Results showed that the NPCK-x samples possessed large surface areas (maximum:2875 m^(2)/g),hierarchical porous structures,and high degree of disorder.N-containing functional groups decomposed during activation process,which could be the dominant reason for appearance of abundant mesopores and well-developed pore structure.Dynamic chlorobenzene adsorption experiments demonstrated that carbon materials with(NH_(4))_(2)C_(2)O_(4)modification exhibited higher adsorption capacity (maximum:1053 mg/g) than those without modification (maximum:723 mg/g).The reusability studies of chlorobenzene indicated that the desorption efficiency of (NH_(4))_(2)C_(2)O_(4)modified porous carbon reached90.40%after thermal desorption at 100℃ under N2atmosphere.Thomas model fitting results exhibited that the existence of mesopores accelerated the diffusion rate of chlorobenzene in porous carbon.Moreover,Grand Canonical Monte Carlo simulation was conducted to verify that micropores with pore sizes of 1.2–2 nm of the optimized porous carbon were the best adsorption sites for chlorobenzene and mesopores with pore sizes of 2–5 nm were also highly active sites for chlorobenzene adsorption.展开更多
Design and synthesis of organic chelating agents containing nitrogen and sulfur as donor atoms and their metal complexes is an interesting field of research for their different types of activities. The bi-dentate N,N ...Design and synthesis of organic chelating agents containing nitrogen and sulfur as donor atoms and their metal complexes is an interesting field of research for their different types of activities. The bi-dentate N,N chelating agent such as 2,2-Bipyridal has been playing a vital role in synthetic and medicinal chemistry. 2,2-Bipyridal has been used to prepare many mixed-ligand complexes. Different ligand complexes prepared from 2,2-Bipyridyl are used in different areas such as molecular catalysis, solar energy conversion, calorimetric analysis, herbicides, molecular recognition, self-assembly, antineoplastic agents, and nucleic acid probes. Another important property of these types of compounds is the triplet state photosensitizing character of bipyridyl nucleus, which is shown in metal complexes. It is also found that compounds containing O,S,N atoms have received considerable attention because of their pharmacological studies like anticancer, antibacterial, and antitumour activities. Therefore, it has been decided to synthesize Schiff bases derived from 2,2’- bipyridyl-5,5’-dicarbaldehyde compounds with O,S,N and F-containing amines and study their antibacterial properties. Several new Schiff bases have been synthesized and fully characterized by spectral data. This paper presents the synthesis and characterization of newly designed Schiff bases.展开更多
文摘Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N_(2)-bidentate(note that N_(2)-bidentate site=N^N-bidentate site;N_(2)≠dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N_(2)-bidentate site,a Cu SAC with isolated undercoordinated Cu-N_(2) sites(Cu1.0/N_(2)-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N_(2)-GDY exhibits the highest Faradaic efficiency(FE)of 80.6% for CH_(4) in electrocatalytic reduction of CO_(2) at-0.96 V vs.RHE,and the partial current density of CH_(4) is 160 mA cm^(-2).The selectivity for CH_(4) is maintained above 70% when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N_(2)-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N_(2) sites are more favorable in generating key ^(*)COOH and ^(*)CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N_(2) sites toward efficient electrocatalysis.
基金funded by National Key Research, Development Program of China (No. 2017YFE0301305KYWX-002)Sichuan Science and Technology Program (No. 2021YFSY0015)
文摘Atmospheric pressure plasma jet(APPJ)was used to clean nitrogen-containing carbon films(C–N)fabricated by plasma-assisted chemical vapor deposition method employing the plasma surface interaction linear device at Sichuan University(SCU-PSI).The properties of the contaminated films on the surface of pristine and He-plasma pre-irradiated tungsten matrix,such as morphology,crystalline structure,element composition and chemical structure were characterized by scanning electron microscopy,grazing incidence x-ray diffraction and x-ray photoelectron spectroscopy.The experimental results revealed that the removal of C–N film with a thickness of tens of microns can be realized through APPJ cleaning regardless of the morphology of the substrates.Similar removal rates of 16.82 and 13.78μm min^(-1)were obtained for C–N films deposited on a smooth pristine W surface and rough fuzz-covered W surface,respectively.This is a remarkable improvement in comparison to the traditional cleaning method.However,slight surface oxidation was found after APPJ cleaning,but the degree of oxidation was acceptable with an oxidation depth increase of only 3.15 nm.Optical emission spectroscopy analysis and mass spectrometry analysis showed that C–N contamination was mainly removed through chemical reaction with reactive oxygen species during APPJ treatment using air as the working gas.These results make APPJ cleaning a potentially effective method for the rapid removal of C–N films from the wall surfaces of fusion devices.
基金financial support from the National Natural Science Foundation of China (51764048, 21961030 and 51474191)Yunnan Province Thousand Youth Talents Plan+1 种基金the Application Basis Research Project of Yunnan Province Science and Technology Department (2017FD144)the Key Natural Science Foundation of Yunnan Province China (2018FA28, 2019FY003023 and 2018FH001-007)。
文摘Organic electrode materials are desirable for green and sustainable Li-ion batteries(LIBs) due to their light-weight, low cost, abundance and multi-electron transfer reactions during battery operation. However, the successful utilization of organic electrodes is hindered by their poor electrical conductivity and low cyclic stability. Herein, a facile synthesis of π-conjugated N-containing heteroaromatic hexacarboxylate(Li6-HAT) compound and its electrochemical performance as an anode material in LIBs is reported.The as-synthesized Li6-HAT electrode renders an ultrahigh initial capacity of 1126.3 m Ah g^(-1) at the current density of 100 m A g^(-1). Moreover, π-conjugated N-containing heteroaromatic center provide excellent reversibility of(de)lithiation process, resulting in excellent capacity retention. Furthermore, a combination of density functional theory(DFT) calculations, in-situ Fourier transform infrared(FTIR) and ex-situ X-ray photoelectron spectroscopy(XPS) characterization reveal that the π-conjugated nitrogen and carboxyl oxygen act as electrochemically active sites during the charge/discharge process. The current work provides novel insights into the charge storage mechanism of organic electrodes and opens up avenues for further development and utilization of organic electrodes in Li-ion batteries.
基金supported by the National Natural Science Foundation of China (51862024,51772140,51962023)the Natural Science Foundation of Jiangxi Province (20171ACB21033,20192ACBL21047)。
文摘N-containing Ce_(2)Si_(2.5)Al_(0.5)O_(3.5)N_(3.5)(CeSiAlON) melilite was synthesized at 1550 and 1600℃ for 5 h from CeO_(2),Si,Al,and Al_(2)O_(3) in nitrogen by using Y_(2)O_(3) and transition-metal nitrates(Co(NO_(3))_(2)·6 H_(2) O and Ni(NO_(3))_(2)·6 H_(2)O) as additives.The effects of Y_(2)O_(3) and transition-metal nitrates on the phase,microstructures and photoluminescence properties of CeSiAlON melilite were studied.The incorporation of Y_(2)O_(3) can promote the reaction of raw materials to a low degree,and results in a unit cell shrinkage of CeSiAlON due to the smaller radius of Y atom than that of Ce atom.The transition-metal nitrates can accelerate the reaction clearly and facilitate the formation of CeSiAlON fibers.The photoluminescence(PL) properties of CeSiAlON melilite presents a board violet emission band because of the 5 d-4 f transitions of Ce^(3+),and the additives can enhance the PL emission intensities of specimen significantly.
基金Supported by the National Natural Science Foundation of China(Nos.22172127 and U23A20123)the Fundamental Research Program of Qingyuan Innovation Laboratory(grant number 00522004).
文摘Catalytic transformation of renewable biomass into value-added chemicals is an appealing strategy to upgrade bio-mass resources.Due to the presence of abundant oxygen-containing groups such as hydroxyl and aldehyde,biomass and its derived platform molecules have been served as ideal starting feedstock to synthesize valuable N-containing chemicals through reductive amination.In this mini review,we overviewed the recent advances in the reductive ami-nation of several key bio-platform molecules including hydroxyl carboxylic acids,furfural,5-hydroxylmethyl furfural and levulinic acid,with a focus on the production of amino acids,furan amines and pyrrolidones using thermocataly-sis,electrocatalysis or photocatalysis.Moreover,the functions of active sites and the reaction mechanisms in different catalytic systems are discussed to get insights into the key factors in the reductive amination of biomass resources.
基金the financial support provided by the National Natural Science Foundation of China(Nos.21563012 and 21363008)Jiangsu Provincial Natural Science Foundation of China(No.BK20161188)+1 种基金Jiangxi Natural Science Foundation of China(Nos.20143ACB20003,20162BCB22020 and 20171BCD40009)Jiangxi Provincial Education Department Foundation of China(No.GJJ170371)
文摘Two N-containing borates, BTES and BMES, were synthesized with dodecyl phenol, 2-(N-containing heterocyclic) ethan-1-ol, boric acid, and dibutylamine, and their tribological properties in rapeseed oil(RSO) were investigated using a four-ball tester. The results showed that the load-carrying ability(P_B value) of RSO can be improved by 40.9% and 67.9%, respectively, when using 0.5 wt% BTES and BMES. Moreover, the antiwear and friction-reducing performances of the additive-containing oils increased with the additive concentration. The X-ray photoelectron spectroscopy results of the worn steel ball surfaces showed that BTES and BMES formed protective films, which contained boron oxide, iron oxide, ferrous sulfate, ferrous sulfide(for BMES), and other organic nitrogen compounds, on the metal surfaces. The better load-carrying and antiwear performances of BMES than those of BTES might be due to their different sulfur contents, which result in different tribochemical reaction films on the contact surfaces. The oxidation stability tests showed that BTES and BMES possessed synergistic antioxidation activity with N-phenyl-α-naphthylamine(T531), and consequently, the oxidation activation energy of the oil sample increased by 77.85% and 82.19%, respectively, compared with that of RSO when the oil sample contained 0.05 wt% BTES/BMES and 0.25% T531.
基金supported by the National Natural Science Foundation of China(22162025,22168040)Regional Innovation Capability Leading Program of Shaanxi(2022QFY07-03,2022QFY07-06)Shaanxi Province Training Program of Innovation and Entrepreneurship for Undergraduates(S202210719108,S202110719107,S202010719121)
文摘Paired electrolysis in anion-exchange membrane(AEM)electrolyzers toward the cathodic nitrate reduction reaction(NO_(3)RR)and anodic benzylamine oxidation reaction(BOR)could generate high value-added N-containing compounds simultaneously.The key challenge is to develop bifunctional electrocatalysts with a wide potential window,which can achieve highly efficient conversion of anode and cathode reactants.Herein,Ni_(3)Se_(4)with Se vacancies was prepared and employed as the cathode and anode of AEM electrolyzers for NO_(3)RR and BOR.^(15)N isotope-labeling online differential electrochemical mass spectrometry(DEMS)proved that ammonium was reduced from nitrates and revealed the reaction pathway of NO_(3)RR.The density functional theory calculation clarified that Se vacancies regulate d-band centers,and then further modulate the adsorption energy of adsorbed hydrogen,NO_(3)^(-)and intermediates on the Ni_(3)Se_(4)-60s surface in NO_(3)RR,so as to optimize the hydrogenation of NO_(3)^(-)into ammonia.Moreover,during the BOR,the Se vacancy can promote the adsorption of OH^(-),which is easier to form the active species of Ni OOH.The technical and economic evaluation exhibited that the cost of paired electrolysis is 1.21 times lower and the profit is 1.42 times higher than that of the unpaired electrolysis,which shows the economic attraction of paired electrolysis.This work delivers the guidance for the design of efficient catalysts for paired electrolysis in AEM electrolyzer toward the sustainable synthesis of value-added chemicals.
基金supported by the National Natural Science Foundation of China(Grant Nos.42230808 and 42102148)China Postdoctoral Science Foundation(Grant No.2021M691497)。
文摘Evaluating the hydrocarbon generation potential of highly mature organic matter is a key and critically challenging area of research in petroleum geochemistry. To explore this issue, we used negative ion electrospray ionization-Fourier transform-ion cyclotron resonance-mass spectrometry to investigate the molecular evolution of N-containing compounds in Carboniferous-lower Permian source rocks with a range of maturities in the northwestern Junggar Basin, China. The N1compounds formed from on-fluorescent chlorophyll catabolites(NCCs), which record the characteristics of the residual soluble organic matter. These components remain in the source rocks after hydrocarbon generation and expulsion, and enable evaluation of the hydrocarbon generation potential. The newly defined indexes of molecular evolution, which are the polymerization index P1([DBE 18+DBE 15]/[DBE 12+DBE 9]_N1) and alkylation index R1(RC_(6–35)/RC_(0–5)), combined with the vitrinite reflectance(VR_(o)) and paleo-salinity index(β-carotane/n Cmax), can identify the factors that control the evolution of highly mature organic matter. The main factor for source rocks deposited in a weakly saline environment is the maturity, but for a highly saline environment both the maturity and salinity are key factors. The high salinity inhibits the molecular polymerization of organic matter and extends the oil generation peak. Given the differences in the bio-precursors in saline source rocks, we propose a new model for hydrocarbon generation that can be used to determine the oil generation potential of highly mature organic matter.
基金supported by the National Key R&D Program of China(2022YFB4002700)the National Natural Science Foundation of China(22475071)the Shanghai Science and Technology Committee Rising-Star Program(22QA1403400)。
文摘Herein,a tandem electrocatalytic-catalytic method is employed to produce valuable alanine from nitrate and waste polylactic acid(PLA).Initially,two strategies are proposed to enhance the performance of electrocatalytic NO_(3)^(-)reduction reaction(NO_(3)^(-)RR):optimizing NO_(3)^(-)adsorption and accelerating water dissociation by modulating the cathode electrocatalyst.Fe-regulated Co nanosheets(Fe_(0.33)-Co(OH)_(2)NSs)have been developed as an efficient electrocatalyst,which demonstrate a remarkable Faradaic efficiency(FE)of 98.2%,with a corresponding yield rate of 10.7 mg h^(-1)cm^(-2)for NO_(3)RR to NH_(3)at-0.1 V vs.RHE.Additionally,~95%FEs of NH_(3)at-200 mA cm^(-2)have been maintained for>430 h in the alkaline solution.Subsequently,in situ technologies have been utilized to elucidate the NO_(3)^(-)RR pathways,the structure transformation of the electrocatalysts,and the effects of Fe-induced work function reduction and electron enrichment at Co sites on electrocatalytic activity.Finally,alanine is synthesized by using PLA and the generated NH_(3)as the raw reactants on the Ru/TiO_(2)catalyst,achieving maximum yield and selectivity of 81.3%and 91.8%,respectively,which provides a novel approach to utilize the nitrogen resource and mitigate plastic pollution.
基金supported in part by the National Natural Science Foundation of China(No.320703S9)the 111 Project from Ministry of Education of China and the State Administration of Foreign Export Affairs of China(No.B18056)the Drug Innovation Major Project(No.2018ZX09735002-003).
文摘Sarglanoids A-F,six new sesquiterpenoids belonging to eudesmane(1-5)and eremophilane(6)types,were isolated from the leaves of Sarcandra glabra,a famous traditional Chinese medicine(TCM).Their structures including absolute configurations were elucidated through extensive spectroscopic analysis and electronic circular dichroism(ECD)calculations.Compounds 1-2 were rare N-containing eudesmane-type sesquiterpenoids.Compound 3 exhibited inhibitory activity against nitric oxide(NO)production in lipopolysaccharides(LPS)-induced RAW 264.7 cells with IC_(50) values at 20.00±1.30μmol·L^(-1).These findings provide scientific evidence for sesquiterpenoids as the material foundation of S.glabra.
基金supported by the Natural Science Foundation of China(21922803 and 21776077)the Shanghai Natural Science Foundation(17ZR1407300 and 17ZR1407500)+3 种基金the China Postdoctoral Science Foundation(BX20190116)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning,the Shanghai Rising-Star Program(17QA1401200)the State Key Laboratory of Organic-Inorganic Composites(oic-201801007)the Open Project of State Key Laboratory of Chemical Engineering(SKLChe-15C03 and SKL-ChE-16C05).
文摘Heteroatom-doping of carbocatalysts has been a powerful strategy to remarkably enhance the catalytic performance.Herein,the underlying nature of N promotional effects on peroxymonosulfate(PMS)activation for phenol removal is understood by combining kinetics analysis with multiple techniques.A strategy using mixed acid oxidation of carbon nanotube(CNT)followed by NH3 treatment is employed to yield a series of catalysts with different N-doping contents but similar fraction of sp^(2)-hybridized carbon and defective degree,endowing with a chance to discriminate the dominant N-containing active sites.The multi-sites kinetics analysis suggests the graphitic N-containing sites as the dominant active sites.The mechanism of the surface-bound reactive species is also discriminated as the dominant reaction mechanism.The insights reported here could provide the methodology to fundamentally understand the heteroatom-doping effects of carbocatalysis.
文摘The title compound, [Cu（phen）2（SO4）（H2O）]·0.5C4H4O4·7H2O （phen = 1,10-phe-nan throline and C4H4O4 = fumaric acid）, has been synthesized and characterized by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1^- with a = 11.4827（2）, b = 11.9086（2）, c = 13.77350（10） A, α = 80.6830（10）, β = 66.6480（10）, γ = 64.048000）°, V = 1554.63（4） A^3, Mr = 722.17, Z = 2, Dc = 1.543 g/cm^3,μ = 0.845 mm^-1, F（000） = 750, R = 0.0349 and wR = 0.0837 for 4754 observed reflections （1 〉 2σ（I））. The compound contains a six-coordinated copper（Ⅱ） center, which is surround by four N atoms of two phen ligands （Cu-N distances in the range of 1.997（2）- 2.225（2） A）, one sulfate O atom （Cu-O = 2.0037（17） A） and one water O atom （Cu-O（Sw） = 2.719（2） A,） in a distorted octahedral geometry. Extensive hydrogen-bonding interactions are involved in water molecules, ligated sulfate anions and fumaric acid molecules. In addition, π-π interactions via aromatic nitrogen-containing ligands are also discussed. The combination of non-covalent interactions leads to the formation of a 3-D network structure.
基金supported by the National Key Research and Development Program of China (No.2019YFC1805804)。
文摘In this work,hydrothermal technique combined with KOH activation were employed to develop a series of porous carbons (NPCK-x) using tobacco stem as a low-cost carbon source and (NH_(4))_(2)C_(2)O_(4)as a novel nitrogen-doping agent.Physicochemical properties of NPCK-x were characterized by Brunauer-Emmett-Teller,field emission scanning electron microscopy,X-ray diffraction,Raman microscope,elemental analysis,and X-ray photoelectron spectroscopy.Results showed that the NPCK-x samples possessed large surface areas (maximum:2875 m^(2)/g),hierarchical porous structures,and high degree of disorder.N-containing functional groups decomposed during activation process,which could be the dominant reason for appearance of abundant mesopores and well-developed pore structure.Dynamic chlorobenzene adsorption experiments demonstrated that carbon materials with(NH_(4))_(2)C_(2)O_(4)modification exhibited higher adsorption capacity (maximum:1053 mg/g) than those without modification (maximum:723 mg/g).The reusability studies of chlorobenzene indicated that the desorption efficiency of (NH_(4))_(2)C_(2)O_(4)modified porous carbon reached90.40%after thermal desorption at 100℃ under N2atmosphere.Thomas model fitting results exhibited that the existence of mesopores accelerated the diffusion rate of chlorobenzene in porous carbon.Moreover,Grand Canonical Monte Carlo simulation was conducted to verify that micropores with pore sizes of 1.2–2 nm of the optimized porous carbon were the best adsorption sites for chlorobenzene and mesopores with pore sizes of 2–5 nm were also highly active sites for chlorobenzene adsorption.
文摘Design and synthesis of organic chelating agents containing nitrogen and sulfur as donor atoms and their metal complexes is an interesting field of research for their different types of activities. The bi-dentate N,N chelating agent such as 2,2-Bipyridal has been playing a vital role in synthetic and medicinal chemistry. 2,2-Bipyridal has been used to prepare many mixed-ligand complexes. Different ligand complexes prepared from 2,2-Bipyridyl are used in different areas such as molecular catalysis, solar energy conversion, calorimetric analysis, herbicides, molecular recognition, self-assembly, antineoplastic agents, and nucleic acid probes. Another important property of these types of compounds is the triplet state photosensitizing character of bipyridyl nucleus, which is shown in metal complexes. It is also found that compounds containing O,S,N atoms have received considerable attention because of their pharmacological studies like anticancer, antibacterial, and antitumour activities. Therefore, it has been decided to synthesize Schiff bases derived from 2,2’- bipyridyl-5,5’-dicarbaldehyde compounds with O,S,N and F-containing amines and study their antibacterial properties. Several new Schiff bases have been synthesized and fully characterized by spectral data. This paper presents the synthesis and characterization of newly designed Schiff bases.
